CN112759753A - Preparation method of phosphorus-nitrogen synergistic flame-retardant polyether polyol - Google Patents
Preparation method of phosphorus-nitrogen synergistic flame-retardant polyether polyol Download PDFInfo
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- CN112759753A CN112759753A CN202011579217.4A CN202011579217A CN112759753A CN 112759753 A CN112759753 A CN 112759753A CN 202011579217 A CN202011579217 A CN 202011579217A CN 112759753 A CN112759753 A CN 112759753A
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- polyether polyol
- nitrogen
- synergistic flame
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000003063 flame retardant Substances 0.000 title claims abstract description 59
- 229920000570 polyether Polymers 0.000 title claims abstract description 59
- 239000004721 Polyphenylene oxide Substances 0.000 title claims abstract description 58
- 229920005862 polyol Polymers 0.000 title claims abstract description 58
- 150000003077 polyols Chemical class 0.000 title claims abstract description 58
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 35
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 29
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 16
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000010452 phosphate Substances 0.000 claims abstract description 10
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 6
- 229930006000 Sucrose Natural products 0.000 claims description 6
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 claims description 4
- -1 aromatic phosphate ester Chemical class 0.000 claims description 4
- 239000000600 sorbitol Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043276 diisopropanolamine Drugs 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- VOWPVJACXJNHBC-UHFFFAOYSA-N methyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OC)OC1=CC=CC=C1 VOWPVJACXJNHBC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 21
- 229920002635 polyurethane Polymers 0.000 abstract description 16
- 239000004814 polyurethane Substances 0.000 abstract description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 abstract description 14
- 239000006260 foam Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 229960004793 sucrose Drugs 0.000 description 5
- 239000000571 coke Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 229920005830 Polyurethane Foam Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000011496 polyurethane foam Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000008098 formaldehyde solution Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000004767 nitrides Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2639—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing elements other than oxygen, nitrogen or sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
- C08G18/509—Polyethers having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
- C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to a preparation method of phosphorus-nitrogen synergistic flame-retardant polyether polyol, and belongs to the technical field of hard foam polyether polyol modification. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol takes a compound containing nitrogen and phosphorus and polyol as a composite initiator, and the compound and the polyol are subjected to polymerization reaction with propylene oxide under the action of a catalyst to obtain the phosphorus-nitrogen synergistic flame-retardant polyether polyol; the nitrogen and phosphorus containing compound is obtained by reacting aromatic phosphate, aldehyde and amine in a solvent. The invention has scientific and reasonable design, the prepared product can be applied to the flame retardant field of polyurethane materials, and the prepared product has excellent pentane intersolubility and storage stability.
Description
Technical Field
The invention relates to a preparation method of phosphorus-nitrogen synergistic flame-retardant polyether polyol, and belongs to the technical field of hard foam polyether polyol modification.
Background
The polyurethane material is a polymer containing urethane continuous segments in a molecular structure, and is widely applied to the fields of clothes, shoes and hats, building outer walls, pipelines, aerospace, furniture, automobiles, medical treatment and the like due to the characteristics of strong wear resistance, excellent shock absorption performance, excellent machining performance and the like. However, common polyurethane materials are easy to burn in air, and a large amount of toxic gas and smoke dust are generated in the burning process, which causes great economic loss and casualties, so that certain requirements are also put forward for the flame retardant property of polyurethane materials at home and abroad, and corresponding standard documents are issued everywhere to limit and prohibit the application of non-flame retardant polyurethane materials.
At present, the main approach for improving the flame retardant performance of polyurethane materials is to add flame retardants containing phosphorus, chlorine, bromine and other flame retardant elements. The flame retardant can be divided into two main types of additive flame retardant and structural flame retardant according to different using methods.
The additive type flame retardant is a method for directly adding a flame retardant which does not physically or chemically react with a reactant into plastic in the preparation process of a polyurethane material so that the material has certain flame retardant performance. However, the added flame retardant can reduce the strength machining performance of the material, and the flame retardant can gradually migrate out in the use process of the material, so that the flame retardant effect is reduced and certain harm is caused to the environment.
The polyether polyol is the most common raw material for producing the polyurethane material, and the production process is relatively simple and environment-friendly, and the reaction conditions are mild. In recent years, there has been a lot of research on modifying polyether polyols to achieve structural flame retardancy of polyurethane materials. At present, many flame-retardant polyether polyols exist in the market, but most of the flame-retardant polyether polyols circulating in the market achieve the flame-retardant effect by introducing halogen. The polyurethane material prepared from the halogen-containing flame-retardant polyether polyol can generate a large amount of smoke and various toxic and harmful gases during combustion, and people are easily suffocated and die when a fire disaster occurs, so that the degree of the fire disaster is increased.
The phosphorus-nitrogen synergistic flame-retardant polyether is a novel environment-friendly flame-retardant polyether, and a polyurethane material produced by the polyether can contain phosphorus and nitrogen simultaneously, and the phosphorus and the nitrogen are connected through a certain chemical structure. It is believed that in the high temperature or polyurethane material combustion process, phosphide and nitride form an intumescent coke layer at high temperature, which acts as a thermal insulating and oxygen barrier protective layer, and nitrogen-containing compounds act as a blowing agent and a coke enhancer, and that the phosphorus-nitrogen flame retardant system can decompose organic compounds at lower temperatures to form coke and water and increase the production of coke residues, thereby enhancing the flame retardant effect. However, the types of phosphorus-nitrogen synergistic flame-retardant polyether sold in the market at present are few, and the synthesis method is complicated. Therefore, the development and application of the phosphorus-nitrogen synergistic flame-retardant polyether are significant.
Disclosure of Invention
The invention aims to provide a preparation method of phosphorus-nitrogen synergistic flame-retardant polyether polyol, which is scientific and reasonable in design, and the prepared product can be applied to the field of flame retardance of polyurethane materials, and has excellent pentane intersolubility and storage stability.
The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol takes a compound containing nitrogen and phosphorus and polyol as a composite initiator, and the compound and the polyol are subjected to polymerization reaction with propylene oxide under the action of a catalyst to obtain the phosphorus-nitrogen synergistic flame-retardant polyether polyol;
the nitrogen and phosphorus containing compound is obtained by reacting aromatic phosphate, aldehyde and amine in a solvent.
Preferably, the aromatic phosphate is one or more of methyl diphenyl phosphate, diphenyl phosphate or triphenyl phosphate.
Preferably, the aldehyde is formaldehyde.
Preferably, the amine is one or more of monoethanolamine, diethanolamine or diisopropanolamine.
Preferably, the solvent is one or more of diethyl ether, methanol, ethanol, ethylene glycol or water.
Preferably, the molar ratio of aromatic phosphate ester, aldehyde and amine is 0.1-1: 0.1-4: 0.1-4.5.
Preferably, when the nitrogen and phosphorus containing compound is prepared, the reaction temperature is 80-105 ℃, and the reaction time is 2-4 h.
Preferably, the polyhydric alcohol is a mixture of two or more of propylene glycol, diethylene glycol, water, glycerol, sorbitol, or sucrose; the catalyst is an organic amine catalyst, and is more preferably N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, pentamethyldiethylenetriamine, N, N, N ', N' -tetramethylalkylenediamine, triethylamine, triethylenediamine, N, N '-diethylpiperazine, DMEA, DBU or N, N' -dimethylpyridine; the alkylene oxide is ethylene oxide or propylene oxide.
Preferably, the amounts of the raw materials used are as follows:
based on the total mass of the four substances as 100 percent.
Preferably, the polymerization temperature is 80-120 ℃ and the polymerization time is 2-8 h.
The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol comprises the following steps:
(1) sequentially adding aromatic phosphate, aldehyde, amine and a solvent into a reaction vessel according to a certain proportion, stirring and reacting for a period of time under a certain condition, removing and recovering the solvent to obtain an initiator containing phosphorus and nitrogen in the structure;
(2) according to different theoretically designed functionalities and hydroxyl values, an initiator containing phosphorus and nitrogen, a polyol and a catalyst in the structure synthesized in the step (1) are subjected to polymerization reaction with alkylene oxide according to a set proportion under a certain condition to generate the phosphorus and nitrogen synergistic flame-retardant polyether polyol.
In the step (1), the stirring speed is preferably 10-25r/min, wherein the aldehyde substance needs to be added dropwise, in batches or directly and completely.
In the step (2), the influence of the type selection of the composite initiator on the polyether indexes is different, and polyether polyols with different index ranges can be synthesized according to the requirements.
According to the invention, aromatic phosphate reacts with amine compounds to generate an initiator containing phosphorus and nitrogen in the structure, the compound is compounded with a certain amount of hard foam polyether polyol initiator to improve indexes such as strength and toughness of foam, and alkylene oxide polymerization is initiated under the action of a catalyst to finally obtain polyether polyols with different indexes; the invention can also introduce the groups which contain hydroxyl, amino and the like and can initiate the polymerization reaction of the alkylene oxide to synthesize polyether polyol, and further participate in the polyurethane reaction to achieve the purpose of flame retardance of the structure. The polyether polyol synthesized by the method has good flame retardant property, higher strength and dimensional stability, and the pentane intersolubility of the product is greatly improved due to the existence of benzene rings in the system.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, the aromatic phosphate reacts with the amine compound to generate the compound containing phosphorus, nitrogen elements and hydroxyl or amino in the structure, so that the functionality of the system is improved, and the flame-retardant component can enter the structure of polyurethane; meanwhile, when the polyurethane material produced by the method is at high temperature or is burnt, the phosphorus element and the nitrogen element in the structure can play a synergistic effect, so that the flame retardant efficiency is improved;
(2) the polyether polyol synthesized by the method has certain autocatalysis activity, and compared with flame-retardant polyester and an additive flame retardant, the polyether polyol has good storage stability and good pentane intersolubility;
(3) the polyurethane foam plastic prepared by the polyether polyol prepared by the method has good flame retardant effect, dimensional stability and higher strength.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the practice of the invention.
The starting materials used in the examples are all commercial products.
Example 1
(1) 249g of methyl diphenyl phosphate, 220g of diethanolamine, 164g of a 37% aqueous formaldehyde solution and 50g of an ether solvent were charged in a three-necked flask equipped with a thermometer, a reflux condenser and a nitrogen guard. Placing on a magnetic heating stirrer, stirring at 22r/min, and reacting at 80 deg.C for 2 h.
(2) The solvent is recovered by rotary evaporation and can be recycled to obtain the initiator containing phosphorus and nitrogen in the structure.
(3) 315g of initiator containing phosphorus and nitrogen, 27.5g of diethylene glycol, 40g of sucrose and 5g of organic amine catalyst in the structure are accurately weighed and added into a reaction kettle, 210g of propylene oxide is slowly dripped into the reaction kettle through a pressure container, the stirring speed is 18r/min, and polymerization reaction is carried out at 100 ℃ to obtain phosphorus and nitrogen synergistic flame-retardant polyether polyol, and the appearance of the polyether polyol is yellow transparent liquid.
Example 2
(1) 250g of diphenyl phosphate, 267g of diisopropanolamine, 164g of a 37% aqueous formaldehyde solution and 50g of an ethanol solvent were placed in a three-necked flask equipped with a thermometer, a reflux condenser and a nitrogen gas guard. Placing on a magnetic heating stirrer, stirring at 22r/min, and reacting at 80 deg.C for 2 h.
(2) The solvent is recovered by rotary evaporation and can be recycled to obtain the initiator containing phosphorus and nitrogen in the structure.
(3) The method comprises the steps of accurately weighing 270g of initiator containing phosphorus and nitrogen, 20g of glycerin, 30g of sorbitol and 5g of organic amine catalyst in a structure, adding the initiator, the glycerin, the sorbitol and the organic amine catalyst into a reaction kettle, slowly dropwise adding 260g of propylene oxide into the reaction kettle through a pressure container, stirring at 18r/min, and carrying out polymerization reaction at 100 ℃ to obtain phosphorus and nitrogen synergistic flame-retardant polyether polyol, wherein the appearance of the phosphorus and nitrogen synergistic flame-retardant polyether polyol is yellow and transparent liquid.
Example 3
(1) In a three-necked flask equipped with a thermometer, a reflux condenser and a nitrogen blanket, 327g of triphenyl phosphate, 122g of monoethanolamine, 164g of 37% formalin solution, and 80g of water were added as a solvent. Placing on a magnetic heating stirrer, stirring at 22r/min, and reacting at 80 deg.C for 2 h.
(2) The solvent is recovered by rotary evaporation and can be recycled to obtain the initiator containing phosphorus and nitrogen in the structure.
(3) 241g of initiator containing phosphorus and nitrogen, 20g of propylene glycol, 35g of sucrose and 5g of organic amine catalyst in the structure are accurately weighed and added into a reaction kettle, 230g of propylene oxide is slowly dripped into the reaction kettle through a pressure container, the stirring speed is 18r/min, and polymerization reaction is carried out at 100 ℃ to obtain phosphorus and nitrogen synergistic flame-retardant polyether polyol, wherein the appearance of the polyether polyol is yellow transparent liquid.
Comparative example 1
Adding 327g of triphenyl phosphate, 50g of methanol solvent, 40g of propylene glycol, 70g of sucrose and 5g of organic amine catalyst into a reaction kettle, slowly dropwise adding 230g of propylene oxide into the reaction kettle through a pressure vessel, stirring at the speed of 18r/min, carrying out polymerization reaction at 100 ℃, discharging materials after the reaction is finished, and recovering and removing the solvent through rotary evaporation to obtain polyether polyol which is light yellow turbid in appearance and contains a large amount of white suspended matters.
The conventional polyether polyol was a light yellow to brownish yellow transparent homogeneous solution, and the polyether polyol prepared in comparative example 1 was pale yellow turbid in appearance and had a large amount of white suspended matter, and could not be used in the next step.
In comparative example 1, the initiator containing phosphorus and nitrogen in the structure is not prepared in advance, triphenyl phosphate is directly added into the polymerization system, and compared with example 3, a flame-retardant structure cannot be introduced into polyether polyol, and the system becomes turbid and white solid is separated out due to the fact that triphenyl phosphate cannot exist stably in the system, so that the system cannot be further detected and used.
Comparative example 2
Adding 265g of cane sugar, 140g of diethylene glycol and 11g of organic amine catalyst into a reaction kettle, slowly and dropwise adding 690g of propylene oxide into the reaction kettle through a pressure container, stirring at 18r/min, carrying out polymerization reaction at 100 ℃, discharging materials after the reaction is finished, and obtaining the polyether polyol which is light yellow transparent liquid in appearance.
The polyether polyols obtained in example 1, example 2, example 3 and comparative example 2 were subjected to hydroxyl number, viscosity and pentane miscibility tests, respectively, and the test results are shown in table 1.
TABLE 1 hydroxyl number, viscosity and pentane miscibility results for polyether polyols obtained in examples 1-3 and comparative example 2
The 4 polyethers are compounded into combined materials according to a certain proportion respectively, and are mixed with PM200 according to a ratio of 1:1.2 respectively for foaming to prepare polyurethane foam, and the results of foam performance testing, combined material proportion and foam performance are shown in Table 2.
Table 2 composition ratios and foam performance results for examples 1-3 and comparative example 2
As can be seen from tables 1 and 2, the phosphorus-nitrogen synergistic flame-retardant polyether polyol prepared by the invention has better pentane intersolubility, and the polyurethane foam plastic prepared by the polyether polyol has higher strength and good flame-retardant effect.
Claims (10)
1. A preparation method of phosphorus-nitrogen synergistic flame-retardant polyether polyol is characterized by comprising the following steps: taking a compound containing nitrogen and phosphorus and polyol as a composite initiator, and carrying out polymerization reaction with propylene oxide under the action of a catalyst to obtain the phosphorus and nitrogen synergistic flame-retardant polyether polyol;
the nitrogen and phosphorus containing compound is obtained by reacting aromatic phosphate, aldehyde and amine in a solvent.
2. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the aromatic phosphate is one or more of methyl diphenyl phosphate, diphenyl phosphate or triphenyl phosphate.
3. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the aldehyde is formaldehyde.
4. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the amine is one or more of monoethanolamine, diethanolamine or diisopropanolamine.
5. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the solvent is one or more of diethyl ether, methanol, ethanol, ethylene glycol or water.
6. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the molar ratio of aromatic phosphate ester, aldehyde and amine is 0.1-1: 0.1-4: 0.1-4.5.
7. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: when the nitrogen and phosphorus containing compound is prepared, the reaction temperature is 80-105 ℃, and the reaction time is 2-4 h.
8. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the polyalcohol is a mixture of more than two of propylene glycol, diethylene glycol, water, glycerol, sorbitol or sucrose, the catalyst is an organic amine catalyst, and the alkylene oxide is ethylene oxide or propylene oxide.
9. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the amounts of the raw materials used were as follows:
based on the total mass of the four substances as 100 percent.
10. The preparation method of the phosphorus-nitrogen synergistic flame-retardant polyether polyol as claimed in claim 1, wherein the preparation method comprises the following steps: the polymerization temperature is 80-120 ℃, and the polymerization time is 2-8 h.
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